CN101910311A - Two component moisture-curable resin combinations and based on tackiness agent, sealing agent and the coating composition of described composition - Google Patents

Two component moisture-curable resin combinations and based on tackiness agent, sealing agent and the coating composition of described composition Download PDF

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CN101910311A
CN101910311A CN2008801238005A CN200880123800A CN101910311A CN 101910311 A CN101910311 A CN 101910311A CN 2008801238005 A CN2008801238005 A CN 2008801238005A CN 200880123800 A CN200880123800 A CN 200880123800A CN 101910311 A CN101910311 A CN 101910311A
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component
moisture
agent
curable resin
silane
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CN101910311B (en
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加里·M·卢卡斯
帕特赖斯·J·莱曼
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General Electric Co
Momentive Performance Materials Inc
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General Electric Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Sealing Material Composition (AREA)

Abstract

A kind of two component moisture-curable resin combinations, described composition comprises: a) moisture free substantially first component, described first component comprises: optional one or more in the resin that (1) is moisture-curable silylated and (2) are selected from following additional component: softening agent, solvent, thixotropic agent, particulate matter, dehumidizier, isocyanic ester scavenging agent, linking agent, adhesion promotor, UV stablizer and antioxidant; With, b) second component, described second component comprises: (1) water, present in an amount at least sufficient to make moisture-curable silylated resin (a) (1) to solidify, (2) at least a softening agent and/or particulate matter, (3) nonionogenic tenside, present in an amount at least sufficient to provide the stable emulsion of softening agent (b) (2) (if existence) and the steady suspension of particulate matter (b) (2) (if existence), (4) Ren Xuan one or more are selected from following additional component: solvent, thixotropic agent, the pH regulator agent, UV stablizer and antioxidant, condition is that described first component and/or described second component also comprise the catalyzer (c) of the condensation reaction of the moisture-curable silylated resin (a) (1) that is used for hydrolysis.

Description

Two component moisture-curable resin combinations and based on tackiness agent, sealing agent and the coating composition of described composition
Background of invention
The present invention relates generally to the moisture-curable resin, more specifically, the present invention relates to two component moisture-curable resin combinations, and its first component contains moisture-curable silylated resin, and its second component contains water.The invention still further relates to tackiness agent, sealing agent and coating composition based on this two component moisture-curable resin combinations.
Tackiness agent is usually used in connecting or fixing two or more materials or adherent, comprises timber, metal, plastics, pottery, stone, glass, concrete, or the like.The adhesive group that is used for these purposes comprises solvent/resin mixture, Resins, epoxy, latex, urethane, organosilicon, cyanoacrylate, acrylic acid or the like, hot melts in wide technical scope, or the like.This tackiness agent may have one or more shortcomings, for example high volatile volatile organic compound (VOC) content, inflammable, with a class or the multiclass adherent is incompatible, set time is desirably long, bond strength is not enough and the storage time short.Silane-functional resin of having developed multiple moisture-curable solves the many kinds in these defectives.Silane-functional adhesive composition solidifies in two-step approach usually, wherein water (water vapor or liquid water form) and organoalkoxysilane radical reaction are (promptly, hydrolysis), form silanol group, then this silanol group and another kind of similarly reaction of the silanol group of the organoalkoxysilane molecule of hydrolysis or condensation form numerous crosslinked.In mono-component organic silicone tackiness agent formulation, catalyzer is generally used for improving the speed of hydrolysis reaction.In many cases, the absorption of water or water vapor and/or infiltration are the step of rate-constrained in curing or cross-linking process.
Well-known moisture-curable resin combination is as sealing agent and tackiness agent.This composition needed a large amount of time (being generally a couple of days) to come completely solidified before reaching maximum strength usually.Use (assembly line application) (for example, in the window assembling) at fabrication line and utilize in some application of sealing agent and tackiness agent, the sealing agent or the tackiness agent that can form initial strength (green strength) fast used in expectation.Expect very that also storage (deposit) time limit of moisture-curable resin combination before using is long.
Summary of the invention
According to the present invention, a kind of two component moisture-curable resin combinations are provided, described composition comprises:
A) moisture free substantially first component, described first component comprises:
(1) moisture-curable silylated resin and
(2) Ren Xuan one or more are selected from following additional component: softening agent, solvent, thixotropic agent, particulate matter, dehumidizier, isocyanic ester scavenging agent, linking agent, adhesion promotor, UV stablizer and antioxidant; With,
B) second component, described second component comprises:
(1) water presents in an amount at least sufficient to make moisture-curable silylated resin (a) (1) to solidify,
(2) at least a softening agent and/or particulate matter,
(3) nonionogenic tenside presents in an amount at least sufficient to provide the stable emulsion of softening agent (b) (2) (if existence) and the steady suspension of particulate matter (b) (2) (if existence),
(4) Ren Xuan one or more are selected from following additional component: solvent, thixotropic agent, pH regulator agent, UV stablizer and antioxidant,
Condition is that described first component and/or described second component also comprise the catalyzer (c) of the condensation reaction of the moisture-curable silylated resin (a) (1) that is used for hydrolysis.
Aforementioned two component moisture-curable resin combinations are highly stable, as long as its first component that contains moisture-curable silylated resin (a) (1) keeps not moisture substantially.In case two kinds of components of composition are mixed together, and silylated resin (a) (1) is hydrolyzed fast, catalyzing and condensing subsequently is to provide the crosslinked resin of quick formation initial strength.
Two component moisture-curable resin combinations of the present invention make that final user can be in the structure of short aftertreatment set time, packing and shipping assembling, for example, window assembly, and can influence the structure of assembling sharply, therefore, improved the speed of production line and reduce product inventory.Be the stability in storage of the excellence of the present composition to make that before using described composition can store the long period (for example, reaching 18 months), and can not reduce performance for other advantages of final user.
The application's two component moisture-curable resin combinations are particularly suitable for being used for industrial components as tackiness agent and/or sealing agent, particularly for example glass assembling (glazing) application of insulating glass unit (IGU) of window assembly.
Statement used in this application " initial strength " is meant sealing agent, tackiness agent and/or the coating that forms enough elastic strengths and base material bounding force, make and to form structural element, even and, still can keep desired results in short period aftertreatment, packing and shipping, and not deformation too early.
The term " stable " and " stability " that are applicable to two component moisture-curable resin combinations of the present invention are interpreted as being meant under packed state, at ambient temperature, and through the storage time of expection, two kinds of components all can not be carried out the chemical transformation of any obvious degree, for example, under the situation of first component, the viscosity that its silylated resin Composition (a) (1) does not have tangible gelation and/or increases this component, the physics homogeneity of each component of perhaps forming this component is without any obvious variation, for example, under the situation of second component, softening agent (b) (2) and/or optional component (b) (3) do not have perceptible the separation with water (b) (1).
Statement " polyether glycol ", " polyester polyol ", " hydroxyl terminated poly-butadiene ", " polyurethane-polyurea " and " polyureas " comprise the resin of such type, and wherein average weight less than half is derived from one or more copolymerisable monomers different with the common monomer type of naming this resin.Therefore, for example, wherein on average still think polyether glycol by the polyether glycol that the ester units of copolymerization constitutes, similarly, wherein on average still think polyester polyol by the polyester polyol that ether (oxyalkylene) unit of copolymerization constitutes less than the weight of half less than the weight of half.
Except in work embodiment or in addition explanation, be interpreted as being modified by word " pact " in all cases in all numerals of the expression amount of substance described in specification sheets and claims, reaction conditions, time length, amount of substance voltinism matter or the like.
It will also be appreciated that any numerical range of quoting among the application estimates to comprise any combination of the different end points of all subranges in this scope and these scopes or subrange.
Further it should be understood that in specification sheets clear and definite or hint disclosed and/or quote in the claims belong to one group structurally, any compound, material or the material of relevant compound, material or material comprise each single representative and all combinations thereof in this group on forming and/or on function.
Detailed Description Of The Invention
I. first component of two component moisture-curable resin combinations
Moisture-curable silylated resin (a) (1)
First component of the application's two component moisture-curable resin combinations contains moisture-curable silylated resin (a) (1), when being exposed to moisture, be hydrolyzed, with after, so that the resin with certain performance to be provided, specific formulation according to composition can be used for the application as tackiness agent, sealing agent and coating.
The precursor resin that can produce silylated resin (a) (1) can be any in those that become known for preparing moisture-curable silylated resin before this.Appropriate resin comprises polyether glycol (i), polyester polyol (ii), hydroxyl terminated poly-butadiene (iii), hydroxy-end capped and the isocyanate-terminated polyurethane prepolymer that is derived from any aforementioned substances (iv), be derived from the isocyanate-terminated and end capped polyurethane-polyurea of amine (poly-(carbamate-urea) or the polyurethane-urea) prepolymer of polyamine and polyureas prepolymer (v), with the olefinic unsaturated polymer that can carry out hydrosilication (hydrosilation) with silane containing hydrogen (vi), for example, the polyolefine and the polyethers that have terminal ethylenically unsaturated group.Silylated resin (a) (1) can adopt any known or conventional mode silylanizing to obtain by these and similar precursor resin, for example, hydroxy-end capped resin can by with the isocyanato silane reaction by silylanizing, isocyanate-terminated resin can be by having the silane reaction of reactive functional group (for example sulfydryl or amido functional group) and by silylanizing, the olefinic unsaturated polyester can be by reacting under the hydrosilication reaction conditions with silane containing hydrogen by silylanizing to isocyanic ester with having.
Some useful especially silylated resins (a) (1) and preparation thereof are described now more fully.
1. the direct moisture-curable silylated resin that obtains by polyvalent alcohol
Moisture-curable silylated resin (iv) can obtain by polyvalent alcohol and the direct silylanizing of isocyanato silane, described polyvalent alcohol for example, aforementioned polyether glycol (i), polyester polyol (ii) with hydroxyl terminated poly-butadiene any in (iii), and other hydroxy-end capped olefin polymer.The preparation of these silylated polyvalent alcohols can be basically as following to obtaining carrying out as described in the moisture-curable silylated resin by hydroxy-end capped polyurethane prepolymer and isocyanato silane reaction.
2. the moisture-curable silylated urethane resin (SPUR) that obtains by isocyanate-terminated urethane (PUR) prepolymer that is derived from polyethers or polyester polyol
Isocyanate-terminated urethane (PUR) prepolymer can be obtained by one or more polyvalent alcohols (being preferably glycol) and one or more polyisocyanates (being preferably vulcabond) reaction, and the ratio of the two makes resulting prepolymer with isocyanate-terminated.Under the situation of glycol and di-isocyanate reaction, use the vulcabond of molar excess.
The polyvalent alcohol that can be used for preparing isocyanate-terminated PUR prepolymer comprises polyether glycol, polyester polyol (for example hydroxy-end capped polycaprolactone), polyester ether polylol (for example those that are obtained by polyether glycol and 6-caprolactone reaction) and polyester ether polyvalent alcohol (for example reacting those that obtain by hydroxy-end capped polycaprolactone and one or more oxyalkylenes (for example oxyethane and propylene oxide)).
Concrete suitable polyvalent alcohol comprises poly-(oxyalkylene) ether glycol (promptly, polyether glycol), be specially poly-(oxygen ethene) ether glycol, poly-(oxypropylene) ether two pure and mild poly-(oxygen ethene-oxypropylene) ether glycol, poly-(oxyalkylene) ether triol, poly-(tetramethylene) ether glycol, polyacetal, polyhydroxy polycarboxylic acrylate, polyhydroxy polycarboxylic esteramides, polyhydroxy polycarboxylic thioether, polycaprolactone glycol and triol, polybutadiene diol, or the like.In one embodiment of the invention, the polyvalent alcohol that is used to prepare isocyanate-terminated PU prepolymer is that number-average molecular weight (Mn) is about 500g/mol to 25, and 000g/mol gathers (oxygen ethene) ether glycol.In another embodiment of the present invention, the polyvalent alcohol that is used to prepare isocyanate-terminated PUR prepolymer is that equivalent weight is about 1,000g/mol to 20, poly-(oxypropylene) ether glycol of 000g/mol.Also can use the mixture of the multiple polyvalent alcohol of various structures, molecular weight and/or functional group.
The functional group of polyether glycol can be about at the most 8, but preferred functional group is 2 to 4, and more preferably functional group is 2 (being glycol).Specially suitable is the polyether glycol of preparation in the presence of double metal cyanide (DMC) catalyzer, alkali metal hydroxide catalyzer or alkali metal alkoxide catalyst; For example referring to United States Patent (USP) 3,829,505,3,941,849,4,242,490,4,335,188,4,687,851,4,985,491,5,096,993,5,100,997,5,106,874,5,116,931,5,136,010,5,185,420 and 5,266,681, these full patent texts are incorporated herein by reference.The polyether glycol of preparation easily has high molecular and low-unsaturation-degree in the presence of these catalyzer, thinks that these performances cause reflective article of the present invention (retroreflective article) to have improved performance.The number-average molecular weight of preferred, polyethers polyvalent alcohol is about 1, and 000g/mol is to about 25, and 000g/mol is more preferably about 2, and 000g/mol is to about 20, and 000g/mol is also more preferably about 4, and 000g/mol is to about 18,000g/mol.The example that is applicable to the commercially available glycol that gets of the PUR prepolymer that preparation is isocyanate-terminated comprises, but be not limited to, (number-average molecular weight is 8 to ARCOLR-1819,000g/mol), (number-average molecular weight is 4 to E-2204,000g/mol) (number-average molecular weight is 11,000g/mol) with ARCOL E-2211.
Can use in numerous polyisocyanates (being preferably vulcabond) any and composition thereof, so that isocyanate-terminated PUR prepolymer to be provided.In one embodiment, described polyisocyanates can be '-diphenylmethane diisocyanate (" MDI "), polymethylene multi-phenenyl isocyanate (" PMDI "), to the MDI of phenylene vulcabond, naphthalene diisocyanate, liquid carbodiimide modified and derivative thereof, isophorone diisocyanate (" IPDI "), dicyclohexyl methyl hydride-4,4 '-vulcabond, tolylene diisocyanate (" TDI ") particularly 2, the 6-TDI isomer, and fully definite various other aliphatic series and the aromatic polyisocyanate in this area, and combination.
Being used for silylation reactants with above-mentioned isocyanate-terminated PUR prepolymer reaction must contain isocyanic ester is had reactive functional group and at least a facile hydrolysis and crosslinkable subsequently group (for example alkoxyl group).Useful especially silylation reactants is the silane with following general formula:
X-R 1-Si(R 2) x(OR 3) 3-x
Wherein X is for to have reactive group that contains active hydrogen to isocyanic ester, for example-SH or-NHR 4, R wherein 4For H, have 8 carbon atoms at the most the monovalence alkyl or-R 5-Si (R 6) y(OR 7) 3-y, R 1And R 5Identical or different optional contain one or more heteroatomic the have bivalent hydrocarbon radical of 12 carbon atoms at the most, each R respectively do for oneself 2And R 6Have the monovalence alkyl of 8 carbon atoms at the most, each R for identical or different 3And R 7Be the identical or different alkyl of 6 carbon atoms at the most that has, x and y independently are 0,1 or 2 separately.
Concrete silane used in this application comprises various hydrosulphonyl silanes, for example 2-mercaptoethyl Trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane, 2-sulfydryl propyl-triethoxysilicane, 3-sulfydryl propyl-triethoxysilicane, 2-mercaptoethyl tripropoxy silane, 2-mercaptoethyl three sec-butoxy silane, 3-sulfydryl propyl group three tert.-butoxy silane, 3-sulfydryl propyl group three isopropoxy silane, 3-sulfydryl propyl group three octyloxy silane, 2-mercaptoethyl three-2 '-ethyl hexyl oxy silane, 2-mercaptoethyl dimethoxy Ethoxysilane, 3-sulfydryl propyl group methoxy ethoxy propoxy-silane, 3-sulfydryl propyl group dimethoxy-methyl silane, 3-sulfydryl propyl group methoxyl group dimethylsilane, 3-sulfydryl propyl group oxyethyl group dimethylsilane, 3-sulfydryl propyl group diethoxymethyl silane, 3-sulfydryl propyl group cyclohexyloxy dimethylsilane, 4-sulfydryl butyl trimethoxy silane, 3-sulfydryl-3-trimethoxysilyl propyl methacrylate TMOS, 3-sulfydryl-3-methyl-propyl-tripropoxy silane, 3-sulfydryl-3-ethyl propyl-dimethoxy-methyl silane, 3-sulfydryl-2-trimethoxysilyl propyl methacrylate TMOS, 3-sulfydryl-2-methyl-propyl dimethoxy benzene base silane, 3-sulfydryl cyclohexyl-Trimethoxy silane, 12-sulfydryl dodecyl Trimethoxy silane, 12-sulfydryl dodecyl triethoxyl silane, 18-sulfydryl octadecyl Trimethoxy silane, 18-sulfydryl octadecyl methoxyl group dimethylsilane, 2-sulfydryl-2-methylethyl-tripropoxy silane, 2-sulfydryl-2-methylethyl-three octyloxy silane, 2-sulfydryl phenyltrimethoxysila,e, 2-sulfydryl phenyl triethoxysilane, 2-sulfydryl tolyl Trimethoxy silane, 2-sulfydryl tolyl triethoxyl silane, 1-mercapto methyl tolyl Trimethoxy silane, 1-mercapto methyl tolyl triethoxyl silane, 2-mercaptoethyl phenyltrimethoxysila,e, 2-mercaptoethyl phenyl triethoxysilane, 2-mercaptoethyl tolyl Trimethoxy silane, 2-mercaptoethyl tolyl triethoxyl silane, 3-sulfydryl propyl group phenyltrimethoxysila,e and 3-sulfydryl propyl group phenyl triethoxysilane; With various aminosilanes, 3-TSL 8330 for example, the 3-aminopropyltriethoxywerene werene, the amino butyl triethoxyl silane of 4-, N-methyl-3-amino-2-methyl propyl trimethoxy silicane, N-ethyl-3-amino-2-methyl propyl trimethoxy silicane, N-ethyl-3-amino-2-methyl propyl group diethoxymethyl silane, N-ethyl-3-amino-2-methyl propyl-triethoxysilicane, N-ethyl-3-amino-2-methyl propyl group-methyl dimethoxysilane, N-butyl-3-amino-2-methyl propyl trimethoxy silicane, 3-(N-methyl-2-amino-1-methyl isophthalic acid-oxyethyl group)-propyl trimethoxy silicane, N-ethyl-4-amino-3,3-dimethyl-butyl dimethoxy-methyl silane, N-ethyl-4-amino-3,3-dimethylbutyl Trimethoxy silane, N-(cyclohexyl)-3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, aminopropyltriethoxywerene werene, two-(3-trimethoxysilyl-2-methyl-propyl) amine and N-(3 '-trimethoxy-silylpropyl)-3-amino-2-methyl propyl trimethoxy silicane.
Catalyzer is generally used for preparing isocyanate-terminated PUR prepolymer.The preferred condensation catalyst that uses, this is because the also curing of the PUR resin Composition of catalysis curable compositions of the present invention of these condensation catalysts (hydrolysis, crosslinked subsequently).Suitable condensation catalyst comprises the tin salt (for example stannous octoate and stannous acetate) of dialkyltin dicarboxylates (for example dibutyl tin dilaurate and acetate two fourth tin), tertiary amine, carboxylic acid, or the like.In one embodiment of the invention, dibutyl tin dilaurate catalyst is used to prepare the PUR prepolymer.Other available catalyzer comprises and contains zirconium and (for example contain bismuth complex (for example KATXC6212, K-KAT XC-A209 and K-KAT 348, by King Industries, Inc. provides), titanium chelate
Figure BPA00001177069900071
Type derives from DuPont company; With the KR type, derive from Kenrich Petrochemical, Inc.) with other organo-metallic catalyst (catalyzer that for example comprises metal such as Al, Zn, Co, Ni, Fe), or the like.
3. the moisture-curable SPUR resin that obtains by the hydroxy-end capped PUR prepolymer that is derived from polyethers or polyester polyol
Moisture-curable SPUR resin (a) (1) can obtain by hydroxy-end capped PUR prepolymer and isocyanato silane reaction.Can adopt the PUR prepolymer essentially identical mode isocyanate-terminated with above-mentioned preparation, use essentially identical material (being polyvalent alcohol, polyisocyanates and optional catalyzer (preferred condensation catalyst)) to obtain hydroxy-end capped PUR prepolymer, it is hydroxy-end capped that the key distinction is that the ratio of polyvalent alcohol and polyisocyanates causes in resulting prepolymer.Therefore, for example under the situation of glycol and di-isocyanate reaction, use the glycol of molar excess, thereby produce hydroxy-end capped PUR prepolymer.
The available silylation reactants that is used for hydroxy-end capped PUR prepolymer is those materials that contain functional group's (for example 1 to 3 alkoxyl group) of isocyanate-terminated and facile hydrolysis.Suitable silylation reactants is the isocyanato silane with following general formula:
Figure BPA00001177069900081
R wherein 8Contain one or more heteroatomic the have alkylidene group of 12 carbon atoms at the most, each R for choosing wantonly 9Have the alkyl or aryl of 8 carbon atoms at the most, each R for identical or different 10Be the identical or different alkyl of 6 carbon atoms at the most that has, z is 0,1 or 2.In one embodiment, R 8Has 1 to 4 carbon atom, each R 10Identical or different, be methyl, ethyl, propyl group or sec.-propyl, z is 0.
Can be used among the application comprising isocyanato propyl trimethoxy silicane, isocyanato sec.-propyl Trimethoxy silane, isocyanato normal-butyl Trimethoxy silane, isocyanato tert-butyl trimethoxy silane, isocyanato propyl-triethoxysilicane, isocyanato sec.-propyl triethoxyl silane, isocyanato ne-butyltriethoxysilaneand, isocyanato tertiary butyl triethoxyl silane with the concrete isocyanato silane that moisture-curable SPUR resin is provided with aforementioned hydroxy-end capped PUR prepolymer reaction, or the like.
4. the moisture-curable SPUR resin that obtains by the isocyanate-terminated or hydroxy-end capped PUR prepolymer that is derived from hydroxyl terminated poly-butadiene
Moisture-curable SPUR resin (a) (1) can be derived from hydroxyl terminated poly-butadiene, is understood to include wherein any hydroxy-end capped polymkeric substance that the polymkeric substance at least about 50% weight is made of the unit that is derived from divinyl among the application.
In one embodiment, described moisture-curable SPUR resin is by (for example having isocyanate-terminated PUR prepolymer based on polyhutadiene and the silane that has at least one hydrolysable group and isocyanic ester is had reactive functional group, the secondary amino group alkyltrialkoxysilaneand) silylanizing obtains, in another embodiment, carry out silylanizing with isocyanato silane and obtain by having hydroxy-end capped PUR prepolymer with at least one hydrolysable group based on polyhutadiene.
PUR prepolymer based on polyhutadiene is hydroxy-end capped by one or more, optionally hydrogenated, straight or branched polybutadiene homopolymer or multipolymer and organic multiple isocyanate are (for example, organic diisocyanate), randomly react and obtain with one or more other two functional compounds and/or hydroxy-end capped polymkeric substance one, when isocyanate functional group's total yield surpasses the total yield of hydroxy functional group, obtain isocyanate-terminated polyurethane prepolymer, when the total yield of hydroxy functional group surpasses isocyanate functional group's total yield, obtain hydroxy-end capped polyurethane prepolymer.
Can be used for preparing isocyanate-terminated hydroxyl terminated poly-butadiene with hydroxy-end capped polyurethane prepolymer have following those: number-average molecular weight (Mn) is about 500g/mol extremely about 10,000g/mol, be preferably about 800g/mol to about 5,000g/mol, proportion of primary OH groups is about 0.1 to about 6.0meq/g, be preferably about 0.3 to about 1.8meq/g, hydrogenation degree is the olefinic position of 0 to 100% existence, and other monomeric average contents of copolymerization are 0 to about 50% weight.
On average have more than a main primary hydroxyl in each molecule of hydroxy-end capped divinyl of the above-mentioned type, for example, the application is suitable use on average have in each molecule about 1.7 to about 3 or more a plurality of primary hydroxyl.On average have at least about 2 in each molecule of hydroxyl terminated poly-butadiene, preferred about 2.4 to about 2.8 hydroxyls, wherein hydroxyl is mainly on the end allylic positions on master's (that is, the longest usually) hydrocarbon chain of molecule." allyl group " configuration is meant the α-allyl group (that is the terminal hydroxyl of polymkeric substance) and the carbon atom bonding adjacent with double-linked carbon of vinyl carbinol.
The cis-1 of the butadiene polymer of use in the present invention appears, 4, anti-form-1,4 and 1, the molecular weight of the ratio of 2-vinyl unsaturated group, the quantity of hydroxyl and position and butadiene polymer will be influenced by its preparation method, and these details are known in the art.
Therefore hydroxyl terminated poly-butadiene with these characteristics can, make things convenient for and use in this application available from several sources.
Useful hydroxyl terminated poly-butadiene also can be mixed other copolymerisable monomer and the contact adhesive composition prepared therefrom of the performance of the special expectation of one or more the silylated polymkeric substance that can give the application among the application.The monomeric total amount of copolymerization on average is no more than the hydroxyl terminated poly-butadiene multipolymer of 50% weight.Described copolymerisable monomer comprises monoolefine and diene, for example ethene, propylene, 1-butylene, isoprene, chloroprene, 2, and 3-dimethyl-1,3-butadiene, 1, the 4-pentadiene, or the like; With, ethylenically unsaturated monomer, for example vinyl cyanide, methacrylonitrile, vinyl toluene, methyl acrylate, methyl methacrylate, vinyl-acetic ester, or the like.As a kind of selection or in addition, hydroxyl terminated poly-butadiene can with one or more other monomer reactions, so that hydroxy-end capped segmented copolymer to be provided.Described monomer comprises provides 1 of polyether segment, 2-epoxide (for example oxyethane and propylene oxide) and the 6-caprolactone of polyester segment is provided, or the like.
Usually in the presence of catalyzer, prepare isocyanate-terminated PUR prepolymer by excessive organic multiple isocyanate and one or more aforementioned hydroxyl terminated poly-butadiene homopolymer and/or copolymer reaction.Term used in this application " polyisocyanates " is meant the organic compound with two or more isocyanate group.Temperature of reaction is generally about 60 ℃ to about 90 ℃; Reaction times is generally about 4 hours to about 8 hours.
Except the hydroxy-end capped polymkeric substance based on divinyl, reaction mixture also can contain one or more chainextenders and/or one or more other polyvalent alcohols.The example of suitable chainextender is a polyvalent alcohol, for example ethylene glycol, propylene glycol, the third-1,3-glycol, fourth-1,4-glycol, own-1,6-glycol, glycol ether, Triethylene glycol, tetraethylene-glycol, dipropylene glycol, Triethylene glycol, tetraethylene-glycol, dipropylene glycol, tripropylene glycol, three four propylene glycol that contract, or the like.Additional polyvalent alcohol comprises polyether glycol, polyester polyol, polyester ether polylol, polyester ether polyvalent alcohol, polybutadiene diol, polyoxyalkylene diols, polyoxyalkylene triols, polytetramethylene glycol, polycaprolactone glycol and triol, or the like, these materials all have at least two primary hydroxyls.
Suitable organic multiple isocyanate comprises any known and conventional organic multiple isocyanate, the especially organic diisocyanate that can prepare polyether polyols with reduced unsaturation before this.Useful vulcabond comprises, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4 '-phenylbenzene-methane diisocyanate, isophorone diisocyanate, dicyclohexyl methyl hydride-4,4 '-vulcabond, contain 2, the various liquid ditan-vulcabond of 4-and 4,4 '-mixture of isomers, Desmodur
Figure BPA00001177069900101
(Bayer), or the like, and composition thereof.Preferred especially isophorone diisocyanate is used to prepare the application's polyurethane prepolymer.
The appropriate catalyst that can be used for preparing the PUR prepolymer is the tin salt (for example stannous octoate and stannous acetate) of dialkyltin dicarboxylates (for example dibutyl tin dilaurate and acetate two fourth tin), tertiary amine, carboxylic acid, or the like.
In order to prepare isocyanate-terminated PUR prepolymer,, use the isocyanurate equivalent of molar excess (NCO group) at least a little, with isocyanate-terminated polybutadiene homopolymer and/or multipolymer with respect to hydroxyl equivalent (OH group).According to selected concrete hydroxyl terminated poly-butadiene homopolymer and/or multipolymer, optional chainextender and the optional polyvalent alcohol based on non-divinyl, the mol ratio of preferred NCO and OH is about 1.1 to about 4.0.
Hydroxy-end capped PUR can be by organic multiple isocyanate (for example, vulcabond, in for example above-mentioned those any, preferred isophorone diisocyanate) prepares with the excessive selected hydroxyl terminated poly-butadiene homopolymer of stoichiometry and/or copolymer reaction.According to the reactivity of corresponding reactant, can use catalyzer, any in for example above-mentioned those.Temperature of reaction is generally about 60 ℃ to about 90 ℃; Reaction times is generally about 2 hours to about 8 hours.Reaction mixture also can contain one or more chainextenders and/or other polyvalent alcohol, any in for example above-mentioned those.
In order to prepare hydroxy-end capped PUR prepolymer, with respect to NCO isocyanurate equivalent (NCO group), use the hydroxyl equivalent of molar excess (OH group) at least a little, use the hydroxy terminated polybutadiene chain.According to the concrete hydroxyl terminated poly-butadiene of using, the mol ratio of preferred NCO and OH is about 0.3 to about 0.95, more preferably about 0.5 to about 0.90.
The silylanizing of isocyanate-terminated PUR prepolymer can and have at least one hydrolysable group by prepolymer and with at least one isocyanic ester be had reactive functional group (promptly, the group that contains active hydrogen, for example hydroxyl, carboxylic acid, sulfydryl, primary amino or secondary amino group) silane reaction and finish.Preferably, described silane is primary amino silane or the secondary amino group silane with following general formula:
X-R 1-Si(R 2) x(OR 3) 3-x
Wherein X is for to have reactive group that contains active hydrogen to isocyanic ester, for example-SH or-NHR 4, R wherein 4For H, have 8 carbon atoms at the most the monovalence alkyl or-R 5-Si (R 6) y(OR 7) 3-y, R 1And R 5Identical or different optional contain one or more heteroatomic the have bivalent hydrocarbon radical of 12 carbon atoms at the most, each R respectively do for oneself 2And R 6Have the monovalence alkyl of 8 carbon atoms at the most, each R for identical or different 3And R 7Be the identical or different alkyl of 6 carbon atoms at the most that has, x and y independently are 0,1 or 2 separately.
The non-limiting instance of aminosilane that is used for the application's silylanizing step comprises various hydrosulphonyl silanes, for example 2-mercaptoethyl Trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane, 2-sulfydryl propyl-triethoxysilicane, 3-sulfydryl propyl-triethoxysilicane, 2-mercaptoethyl tripropoxy silane, 2-mercaptoethyl three sec-butoxy silane, 3-sulfydryl propyl group three tert.-butoxy silane, 3-sulfydryl propyl group three isopropoxy silane, 3-sulfydryl propyl group three octyloxy silane, 2-mercaptoethyl three-2 '-ethyl hexyl oxy silane, 2-mercaptoethyl dimethoxy Ethoxysilane, 3-sulfydryl propyl group methoxy ethoxy propoxy-silane, 3-sulfydryl propyl group dimethoxy-methyl silane, 3-sulfydryl propyl group methoxyl group dimethylsilane, 3-sulfydryl propyl group oxyethyl group dimethylsilane, 3-sulfydryl propyl group diethoxymethyl silane, 3-sulfydryl propyl group cyclohexyloxy dimethylsilane, 4-sulfydryl butyl trimethoxy silane, 3-sulfydryl-3-trimethoxysilyl propyl methacrylate TMOS, 3-sulfydryl-3-methyl-propyl-tripropoxy silane, 3-sulfydryl-3-ethyl propyl-dimethoxy-methyl silane, 3-sulfydryl-2-trimethoxysilyl propyl methacrylate TMOS, 3-sulfydryl-2-methyl-propyl dimethoxy benzene base silane, 3-sulfydryl cyclohexyl-Trimethoxy silane, 12-sulfydryl dodecyl Trimethoxy silane, 12-sulfydryl dodecyl triethoxyl silane, 18-sulfydryl octadecyl Trimethoxy silane, 18-sulfydryl octadecyl methoxyl group dimethylsilane, 2-sulfydryl-2-methylethyl-tripropoxy silane, 2-sulfydryl-2-methylethyl-three octyloxy silane, 2-sulfydryl phenyltrimethoxysila,e, 2-sulfydryl phenyl triethoxysilane, 2-sulfydryl tolyl Trimethoxy silane, 2-sulfydryl tolyl triethoxyl silane, 1-mercapto methyl tolyl Trimethoxy silane, 1-mercapto methyl tolyl triethoxyl silane, 2-mercaptoethyl phenyltrimethoxysila,e, 2-mercaptoethyl phenyl triethoxysilane, 2-mercaptoethyl tolyl Trimethoxy silane, 2-mercaptoethyl tolyl triethoxyl silane, 3-sulfydryl propyl group phenyltrimethoxysila,e and 3-sulfydryl propyl group phenyl triethoxysilane; With various aminosilanes, 3-TSL 8330 for example, the 3-aminopropyltriethoxywerene werene, the amino butyl triethoxyl silane of 4-, N-methyl-3-amino-2-methyl propyl trimethoxy silicane, N-ethyl-3-amino-2-methyl propyl trimethoxy silicane, N-ethyl-3-amino-2-methyl propyl group diethoxymethyl silane, N-ethyl-3-amino-2-methyl propyl-triethoxysilicane, N-ethyl-3-amino-2-methyl propyl group-methyl dimethoxysilane, N-butyl-3-amino-2-methyl propyl trimethoxy silicane, 3-(N-methyl-2-amino-1-methyl isophthalic acid-oxyethyl group)-propyl trimethoxy silicane, N-ethyl-4-amino-3,3-dimethyl-butyl dimethoxy-methyl silane, N-ethyl-4-amino-3,3-dimethylbutyl Trimethoxy silane, N-(cyclohexyl)-3-TSL 8330, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, aminopropyltriethoxywerene werene, two-(3-trimethoxysilyl-2-methyl-propyl) amine and N-(3 '-trimethoxy-silylpropyl)-3-amino-2-methyl propyl trimethoxy silicane.
For many application, those application that for example are used to seal and be coated with, preferred PUR prepolymer is basically fully by silylanizing, promptly, all or all basically isocyanate group and silane reaction are to provide complete basically silylated polyether polyols with reduced unsaturation.
The silylanizing of hydroxy-end capped PUR prepolymer can be finished by prepolymer and isocyanato silane (for example, specified in those any) reaction.
When silylated resin was desired to be used for sealing and coating and used, the silylanizing of preferred aforementioned hydroxy-end capped PUR prepolymer based on polyhutadiene was complete basically,, does not have hydroxyl basically after silylanizing that is.
About the silylated details of other hydroxy-end capped alkene, can be with reference to United States Patent (USP) 4,975,488, this full patent texts is incorporated herein by reference.
5. the moisture-curable silylated resin that obtains by the silylanizing isocyanate-terminated or end capped urethane of amine and/or polyureas prepolymer that is derived from polyamine
Isocyanate-terminated in its polymer chain, contain one or more amino-formate bonds and one or more urea key, and isocyanate-terminated contain the urea key with the end capped polyureas of amine main (if not exclusively) in its polymer chain with the end capped polyurethane-polyurea of amine (poly-(carbamate-urea) or polyurethane-urea) prepolymer.Two types prepolymer is known in the art.Can use isocyanic ester-reactive silane to carry out the silylanizing of isocyanate prepolymer, with can use isocyanato silane to carry out the silylanizing of amino-terminated prepolymer, this is as above-mentioned described about hydroxy-end capped silylanizing with isocyanate-terminated precursor resin.
6. the moisture-curable silylated resin that obtains by the hydrosilication of resin with terminal ethylenically unsaturated group
Moisture-curable silylated resin (a) (1) can be by having terminal ethylenically unsaturated group polymkeric substance and the hydrosilication of silane containing hydrogen (silane containing hydrogen or hydrogen silane) obtain, for example, particularly in aforesaid U.S. Patent 4,975,488 and United States Patent (USP) 4,371,664; 4,334,036; 5,298,572; 5,986,014; 6,274,688; 6,420,492; 6,552,118; 7,153,911; 7,202,310; With 7,223, those described in 817, these full patent texts are incorporated herein by reference.
Moisture-curable silylated resin (a) (1) can constitute first component whole of the application's two components compositions, but one or more optional components (a) (2) of preferred combination, for example, softening agent, particulate filler, or the like, wherein in per 100 weight part mixtures, the content that is present in the silylated resin in the mixture is the 10-80 weight part, is preferably the 20-50 weight part.
Optional component (a) (2) and (b) (4)
As mentioned above, first component of two component moisture-curable compositions of the present invention also can contain the optional component (a) (2) of one or more known and convention amounts, and that wherein can mention has softening agent, solvent, thixotropic agent, particulate matter, dehumidizier, isocyanic ester scavenging agent, linking agent, adhesion promotor, UV stablizer and an antioxidant.Similarly, second component of described composition also can contain one or more optional components (b) (4), and wherein one material can be identical or different with above-mentioned optional component (a) (2).Therefore, optional component (b) (4) comprises solvent, thixotropic agent, pH regulator agent, UV stablizer and antioxidant, also is to use with known and convention amount.
As an alternative, or except particulate matter, be applicable to that first component of the optional two component moisture-curable compositions that add the application to and the example of the softening agent in second component thereof comprise phthalic ester, dipropylene glycol dibenzoate and glycol ether dibenzoate and composition thereof, epoxidised soybean oil, or the like.Dioctyl phthalate (DOP) and Di Iso Decyl Phthalate can be available from Exxon Chemical, commodity Jayflex DOP by name and JayFlex DEDP.Dibenzoate can derive from Velsicol Chemical Corporation, and commodity are called Benzoflex 9-88, Benzoflex9-88SG, Benzoflex 50 and Benzoflex 400.Epoxidised soybean oil is for deriving from the Flexol EPO of HoughtonChemical Corporation.In the gross weight of the composition of per 100 weight parts, the content that can be present in the softening agent in the application's the two component moisture-curable compositions is the 0-50 weight part, is preferably the 5-15 weight part.
Useful solvent comprises aromatics and aliphatic ester and ketone, and in the gross weight of per 100 weight parts moisture-curable composition of the present invention, the amount of solvent is the 0-20 weight part, is preferably the 0-5 weight part.
Exemplary useful thixotropic agent is the clay and the polymeric amide of various castor wax, pyrogenic silica, processing.In the gross weight of per 100 weight part the application's two components compositions, these optional additives are generally the 0-10 weight part, are preferably the 0.1-2 weight part.Thixotropic agent comprises and derives from following those: Aerosil derives from Degussa; Cabo-Sil TS 720 derives from Cabot; Castorwax derives from CasChem; Thixatrol and Thixcin derive from Rheox; Crayvallac derives from CrayvalleyCorp.; And Dislon, derive from King Industries.If thixotropic agent has reactivity to silane (for example, silicon-dioxide), may need to regulate the amount of preparation to carry out equilibrium.
As an alternative, or except softening agent, be applicable to that first component of the optional two component moisture-curable compositions that add the application to and the typical particulate matter (for example, filler) of second component thereof comprise pyrogenic silica, precipitated silica and lime carbonate.Granularity is that the lime carbonate of processing of 0.07 μ-4 μ is particularly useful, and can be available from several commodity: Ultra Pflex, the SuperPflex of Specialty in Minerals, Hi Pflex; Winnofil SPM, the SPT of Solvay; The Hubercarb lat of Huber, Hubercarb 3Qt and Hubercarb W; The Kotomite of ECC; Omyacarb FT and BLR-3 with Omya.In the gross weight of the composition of per 100 weight parts, the content that can be present in particulate matter in the two component moisture-curable compositions (for example aforementioned any) is the 0-70 weight part, is preferably the 40-60 weight part.
Optional from the known and conventional silane that is used for these effects arbitrarily before this any of suitable dehumidizier, linking agent and adhesion promotor.Preferred dehumidifying silane is vinyl silanes, for example, and vinyltrimethoxy silane (Silquest* A-171 silane) and methyltrimethoxy silane (Silquest* A-1630 silane).Useful crosslinked silane and help sticking silane to comprise γ-glycidoxypropyltrime,hoxysilane (Silquest *A-187 silane), gamma-amino propyl trimethoxy silicane (Silquest* A-1110 silane), N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane (Silquest* A-1120 silane), two-(γ-trimethoxy-silylpropyl) amine (Silquest *A-1170 silane), N-β-(amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane (Silquest* A-2120 silane) and three-(γ-trimethoxysilyl) chlorinated isocyanurates (Silquest *A-Link TM597 silane).These silane derive from the registered trademark of MomentivePerformance Materials.Usually, in described first component of per 100 weight parts, first component of two component moisture-curable compositions of the present invention can contain the 0-7 weight part, this silane of preferred 1-5 weight part.
Preparing in the moisture-curable silylated resin (a) (1) by hydroxy-end capped resin and above-mentioned isocyanato silane reaction, between the shelf lives of first component of the application's two components compositions, a small amount of isocyanate group with can follow the possible hydroxyl of described silylated resin to react, and degree according to its reaction, for example, may comprise isocyanic ester and hydroxy-end capped resin (if, after silylanizing, still have hydroxyl) further reaction, the H-H reaction of isocyanic ester and carbamate groups forms allophanate, the atomic reaction of hydrogen of isocyanic ester and urea groups forms biuret, and hydroxy-end capped resin and alkoxysilyl reaction, these reactions can cause the viscosity of silylated resin to increase to making the very degree of difficulty of using of described two components compositions, and under the situation about in by manual operation case (hand-operated cartridge), manually using, if it is can not reach average intensity separately, then impracticable.For fear of or alleviate this problem, preferably in the first component formulation, comprise isocyanic ester-reactive scavenging agent, the sequence number that these isocyanic ester-reactive scavenging agent is disclosed in the common pending trial of the common transfer of submitting on September 21st, 2006 is 11/524, in 844 the U.S. Patent application [agent docket: 1302-142], this patent application is incorporated herein by reference in full.Disclosed as the application, isocyanic ester-reactive scavenging agent has at least one active hydrogen, rise than obvious any in the reaction of not expecting of increase of the viscosity of first component of two components compositions that can cause the application, isocyanic ester-reactive scavenging agent will be with bigger speed and isocyanate reaction.Suitable isocyanic ester-scavenging agent comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol, and composition thereof.These content with similar isocyanic ester-scavenging agent that can be incorporated in the first component formulation are the 0.01-0.5 weight part, are preferably the 0.02-0.2 weight part, based on the moisture-curable silylated resin (a) (1) of 100 weight parts.
Known and conventional UV stablizer and/or antioxidant can common content be incorporated in the application's first component of two components compositions, for example, in described first component of per 100 weight parts, UV stablizer and/or oxidation resistant content are the 0-10 weight part, are preferably the 0-4 weight part.Such suitable material derives from Ciba-Geigy, and commodity are called Tinuvin 770, Tinuvin 327, Tinuvin 213, Tinuvin 622 and Irganox 1010.
II. second component of two component moisture-curable resin combinations
Water (b) (1)
The water that can use any industrial suitable source is with the water component of two component moisture-curable resin combinations that the application is provided, and condition is that it does not conform to the molten and/or insoluble material that any significant quantity can influence the performance of the cured resin that the mixture by two kinds of components obtains unfriendly.Deionized water is generally used for most of formulations.
The amount of contained water depends on the amount and the character of moisture-curable silylated resin (a) (1) contained in first component to a great extent in second component.Generally speaking, in second component of per 100 weight parts two components compositions of the present invention, the amount of the water in second component can be the 0.1-40 weight part, is preferably the 1-20 weight part.
Softening agent and/or particulate matter (b) (2)
Softening agent, particulate matter that second component of two components compositions contains appropriate amount are (for example, filler, fortifying fibre, or the like) or the two, identical or different with the softening agent of above specified optional components as first component and in the particulate matter any.Multiple factor is depended in the selection of the concrete consumption of softening agent and/or particulate matter in two components compositions of the present invention, for example the rheological property of first component, in first component, whether have the rheological property of any softening agent and particulate matter, the expectation of second component and similarly consider.Generally speaking, second component in per 100 weight parts, two components compositions can contain the 0-80 weight part, the softening agent and/or the 0-60 weight part of preferred 20-60 weight part, the particulate matter of preferred 30-50 weight part.
Nonionogenic tenside (b) (3)
It is important keeping the stability in storage of second component of two components compositions of the present invention, described second component contains at least a nonionogenic tenside of q.s, to prevent softening agent or particulate matter (b) (2) and/or following optional component (b) (3) and water (b) (1) any obvious or perceptible separation.Be included in suitable ionic surfactant pack in second component and draw together the multipolymer of Viscotrol C, oleic acid ethoxylate, alkylphenol ethoxylate, oxyethane (EO) and the propylene oxide (PO) of polyoxyethylene glycol, polypropylene glycol, ethoxylation, preferably, the multipolymer of organosilicon and polyethers (for example, being derived from the polyethers of oxyethane, propylene oxide and composition thereof).Use organic silicon polyether to be described in United States Patent (USP) 5,744,703 as nonionogenic tenside, this full patent texts is incorporated herein by reference.The consumption of nonionogenic tenside (b) (3) will be enough to keep the stability in storage of the second component expected time, and its suitable consumption is subjected to influence of various factors, for example the amount of the optional components of water, softening agent, particulate matter and formation second component.The optimum quantity that is used for the nonionogenic tenside of the second concrete component formulation can easily adopt the normal experiment method to determine.Generally speaking,, can contain the 0.1-40 weight part, the nonionogenic tenside (b) (3) of preferred 1-30 weight part in per 100 weight parts, second component.
Catalyzer (c)
At least one component of the application's two components compositions contains the catalyzer (c) of the condensation reaction of the moisture-curable silylated resin (a) (1) that is useful on hydrolysis.Usually, catalyzer (c) is incorporated in first component of two components compositions.But, if this catalyzer (c) is a hydrolysis-stable, then catalyzer (c) or its part can be incorporated in second component, still, doing does not like this have technical advantage usually.
Catalyzer (c) can be known in those crosslinked compounds of acceleration in moisture-curable tackiness agent, sealing agent and the coating any of being used in.Described catalyzer can comprise metal and nonmetallic compound.The example that can be used for metal condensation cure catalyst of the present invention comprises the compound of tin, titanium, zirconium, lead, iron, cobalt, calcium halophosphate activated by antimony andmanganese, bismuth and zinc.Can be used for promoting the crosslinked tin compound of the silylated polyurethane composition of two components of the present invention to comprise: nonchelated tin compound, for example dibutyl tin dilaurate, oxalic acid two fourth tin, dimethanol two fourth tin, two neodecanoic acid methyl-tins, stannous octoate and dibutyl tin oxide.In another embodiment, use two B-two ketone acids two organic radical tin.Preferred two B-two ketone acids two organic radical tin are two-acetopyruvic acid two fourth tin.Other example of tin compound can be referring to United States Patent (USP) 5,213, and 899,4,554,338,4,956,436 and 5,489,479, these full patent texts are incorporated herein by reference.In the embodiment, use the titanium compound of chelating again, for example, two (ethyl acetoacetic acids) 1,3-propane dioxy base titanium; Two (ethyl acetoacetic acid) diisopropoxy titanium; And tetralkyl titanate, for example tetra-n-butyl titanate and titanium isopropylate.Preferred condensation catalyst of the present invention is a metal catalyst.Preferred metal condensation catalyst is preferably selected from tin compound, wherein preferred dibutyl tin dilaurate and " chelating " dibutyl tin oxide (Fomrez TMSUL 11A).
The component (d) that other is optional
One or both components of the application's two components compositions can contain the optional component that one or more are not above-mentioned those, and certainly, condition is that concrete optional component is compatible fully with the component of waiting to mix wherein.These other optional component (d) comprises known and other resin convention amount, for example, curable resin (for example Resins, epoxy, acrylate and methacrylate resin, urethane, silanol stopped poly-diorganosiloxane, or the like), be used for curing catalysts, defoamer, viscosity control agent, spices, pigment, tinting material, biocide, biostat, the spices of described resin, or the like.
Moisture-curable silylated resin combination of the present invention can be prepared as tackiness agent, sealing agent, coating, packing ring, industrial rubber product, or the like.In order to be mixed with encapsulant composition, silylated resin combination of the present invention and known filler of prior art that is used for elastic composition and additive combination are used.By adding these materials, can reach specific physicals, for example viscosity, flow rate, hang (sag) from above, or the like.
First component of two components compositions of the present invention can be prepared as follows, for example, adopt intermittently or preparation mode continuously, with moisture-curable silylated resin, optional component (for example softening agent, particulate matter, or the like) and/or catalyzer thorough mixing together.
In interrupter method, use double planetary mixer, the twin screw extruder of configuration high-speed decollator, and/or Hauschild SpeedMixer TMCan be with each composition of first component of two components compositions uniform mixing basically.Usually, with moisture-curable silylated resin and optional component under 60 ℃ to 90 ℃ uniform mixing 60-90 minute basically.Be cooled to be lower than 50 ℃ after, can add silane adhesion promotor, linking agent and curing catalysts, and under the exsiccant nitrogen atmosphere, with composition remix 10 minutes to 60 minutes.With about 5 minutes to 60 minutes of composition vacuum outgas, packing was finished first component subsequently subsequently.Adopt similar mode, water, softening agent, particulate matter, nonionogenic tenside and optional component water are mixed together about 10 minutes to 60 minutes under 20 ℃ to 70 ℃.With composition vacuum outgas 5 minutes to 60 minutes, packing was finished second component subsequently.
In continuous preparation method, all the components that constitutes a kind of component can be mixed in the forcing machine that is mixed continuously, to produce compositions desired of the present invention.The forcing machine that is mixed continuously can be any forcing machine that is mixed continuously, for example twin screw Werner-Pfleiderer/Coperion forcing machine, Buss or P.B.Kokneader forcing machine.In this continuous processing, forcing machine at 50 ℃ to 100 ℃, is more preferably operated under 60 ℃ to 80 ℃ the temperature usually, preferably operates under vacuum, to remove issuable volatile matter in the married operation process.
Provide following examples to be used to illustrate the present invention.In each embodiment, all parts and/or per-cent are weight part (pbw).In all embodiments, use the forcing machine that is mixed continuously to prepare the moisture-curable silylated resin combination of two components.This continuous extruder is 30mm Coperian (being called a Werner-Pfleiderer in the past) twin screw extruder.The moisture-curable silylated resin combination of resulting two components shows excellent stability in storage, fast setting and excellent autoadhesion characteristic.In all embodiments, use the ratio of mixture of 10% volume, first ratio of component, 1% volume, second component that two components compositions are mixed.Use pneumatic 10: 1 volume cascade tube spreader rifles (tandemcartridge application gun, MixPac being equipped with static mixer TM, DP 200-70 model, ConProTec Inc.) and 10: 1 ratio of mixture of realization.
By measure in 50 ℃ down store 6 months before, among and the viscosity of afterwards composition, test each in first component and second component.Composition is packaged in the aluminium of sealing, and is placed in 50 ℃ of baking ovens.With a month interval measurement viscosity.According to the modulus under 50% elongation of ASTM D-412 test composition, according to the hardness of ASTM C-661 test composition, according to the stretching adhesion (adhesion) of ASTM C-1135 test composition, according to the lap shear adhesion of ASTM C-961 test composition.All adherence tests are carried out on unprimed PVC base material, and this base material is with soap and water cleaning, dry then, subsequently applied adhesives.All adhesions and physical property test are carried out on InstronModel 4465 trier.
Embodiment 1
A. the preparation of first component of two components compositions
In the machine barrel 1 of forcing machine, import 30.6pbw SPUR continuously TMThe precipitated chalk (SpecialtyMinerals Corp.) that 1015 resins (MomentivePerformance Materials), 15.4pbw UltraPflex handled, water-ground limestone (ground calciumcarbonate) (Specialty Minerals Corp.) and 1.1pbw Crayvallac SLX polymeric amide thixotropic agent (Crayvalley Corp) that 41.6pbw Hi-Pflex 100 handled.On forcing machine, add other downstream material continuously: 9.3pbw Di Iso Decyl Phthalate, 1pbw vinyltrimethoxy silane (Silquest*A-171 silane) dehumidizier, 1pbwN-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane (Silquest*A-1120 silane) adhesion promotor and 0.07pbw dibutyl tin dilaurate condensation cure catalyst.The processing temperature of forcing machine remains on 80 ℃, and throughput rate is 40lb/hr.The vacuum that will outgas (25 inches Hg) is applied to the machine barrel 10 of forcing machine.The purified first component formulation directly is extruded into high density polyethylene(HDPE) Semco TMTube (deriving from PRC-DeSoto) and sealing.
B. the preparation of second component of two components compositions
Continuous input 40pbw Di Iso Decyl Phthalate, 20pbwUltraPflex handled in the machine barrel 1 of forcing machine precipitated chalk (Specialty Minerals Corp.) and 20pbw titania powder.On forcing machine, add other downstream material continuously: the 20pbw pre-composition that comprises 50pbw SF1288 silicone polyether surfactant and 50pbw water.The processing temperature of forcing machine remains on 80 ℃, and throughput rate is 40lb/hr.The vacuum that will outgas (25 inches Hg) is applied to the machine barrel 10 of forcing machine.The purified second component formulation directly is extruded into high density polyethylene(HDPE) Semco TMTube and sealing.50 ℃ of stability tests the results are shown in following table 1.
C. two components compositions of He Binging
Use the two thorax rifles (duel chamber gun) of MixPac, first component is mixed with 10: 1 volumetric mixture ratios with second component.Modulus, hardness, stretching adhesion and lap shear adherence test the results are shown in following table 2-6.
Embodiment 2
Repeat embodiment 1, but be to use 0.13pbw dibutyl tin dilaurate condensation cure catalyst to prepare first component.50 ℃ of stability tests of second component the results are shown in following table 1.Modulus, hardness, stretching adhesion and lap shear adherence test the results are shown in following table 2-6.
Embodiment 3
Repeat embodiment 1, but be to use 0.23pbw dibutyl tin dilaurate condensation cure catalyst to prepare first component.50 ℃ of stability tests of second component the results are shown in following table 1.Modulus, hardness, stretching adhesion and lap shear adherence test the results are shown in following table 2-6.
Embodiment 4
Repeat embodiment 1, but be to use 0.07pbw Fomrez TMSUL 11-A (Chemtura) condensation cure catalyst prepares first component.50 ℃ of stability tests of second component the results are shown in following table 1.Modulus, hardness, stretching adhesion and lap shear adherence test the results are shown in following table 2-6.
Embodiment 5
Repeat embodiment 2, but be to use 0.13pbw Fomrez TMSUL 11-A condensation cure catalyst prepares first component.50 ℃ of stability tests of second component the results are shown in following table 1.Modulus, hardness, stretching adhesion and lap shear adherence test the results are shown in following table 2-6.
Embodiment 6
Repeat embodiment 2, but be to use 0.23pbw Fomrez TMSUL 11-A condensation cure catalyst prepares first component.50 ℃ of stability tests of second component the results are shown in following table 1.Modulus, hardness, stretching adhesion and lap shear adherence test the results are shown in following table 2-6.
Comparative Examples 1
This embodiment illustrates the continuous production of the silylated polyurethane binder of single component that uses the 0.07pbw dibutyl tin dilaurate, stability in storage, modulus, hardness, stretching adhesion and lap shear adhesion the results are shown in following table 1-6.
Comparative Examples 2
This embodiment explanation contains two component S PUR of some SPUR resin TMThe continuous production of second component of binder composition.
In the machine barrel 1 of forcing machine, import 5pbw SPUR continuously TMPrecipitated chalk that 1015 resins, 35pbw Di Iso Decyl Phthalate, 20pbw UltraPflex handled (Specialty MineralsCorp.) and 20pbw titania powder.Add other downstream material continuously to forcing machine: the 20pbw pre-composition that comprises 50pbw SF1288 silicone polyether surfactant and 50pbw water.The processing temperature of forcing machine remains on 80 ℃, and throughput rate is 40lb/hr.The vacuum that will outgas (25 inches Hg) is applied to the machine barrel 10 of forcing machine.The purified second component formulation directly is extruded into high density polyethylene(HDPE) Semco TMTube and sealing.50 ℃ of stability tests the results are shown in following table 1.
Show 1:50 ℃ of accelerated deterioration stable storing Journal of Sex Research
* use Brookfield HBT Heliopath, Spindle TC obtains viscosity measurement under 5rpm
Stability data explanation in the table 1 only can not reach storage time (packing) stability when hydrolyzable SPUR resin does not contact with moisture with silane.
Table 2: ASTM D-412 modulus under 50% elongation and the relation of set time
Table 3:ASTM C-661 hardness, the relation of Shore A and set time
Figure BPA00001177069900213
* use the Exacta that derives from New Age Industries TMThe hardness that testing machine obtains, the Shore A measuring result
The relation that table 4:ASTM C-1135 stretches adhesion and set time
Figure BPA00001177069900221
The relation that table 5:ASTM C-1135 stretches adhesion and set time
Figure BPA00001177069900222
Table 6:ASTM C961: lap shear adhesion and the relation of set time
Figure BPA00001177069900223
Data among the table 2-6 show that compared with identical single component formulation, the solidification rate of two component formulations is obviously very fast.
With reference to this specification sheets or the disclosed practice of the present invention of the application, other embodiment of the present invention it will be apparent to those skilled in the art that.Expection specification sheets and embodiment regard and only are used to illustrate that true scope of the present invention and spirit are limited by following claim as.

Claims (25)

1. component moisture-curable resin combination, described composition comprises:
A) moisture free substantially first component, described first component comprises:
(1) moisture-curable silylated resin and
(2) Ren Xuan one or more are selected from following additional component: softening agent, solvent, thixotropic agent, particulate matter, dehumidizier, isocyanic ester scavenging agent, linking agent, adhesion promotor, UV stablizer and antioxidant; With,
B) second component, described second component comprises:
(1) water presents in an amount at least sufficient to make moisture-curable silylated resin (a) (1) to solidify,
(2) at least a softening agent and/or particulate matter,
(3) nonionogenic tenside presents in an amount at least sufficient to provide the steady suspension of the stable emulsion of the softening agent (b) (2) when existing and the particulate matter (b) (2) when existing,
(4) Ren Xuan one or more are selected from following additional component: solvent, thixotropic agent, pH regulator agent, UV stablizer and antioxidant,
Condition is that described first component and/or described second component also comprise the catalyzer (c) of the condensation reaction of the moisture-curable silylated resin (a) (1) that is used for hydrolysis.
2. two component moisture-curable resin combinations of claim 1, wherein moisture-curable silylated resin (a) (1) is obtained by at least a silylanizing that is selected from following resin: polyether glycol (i), polyester polyol (ii), hydroxyl terminated poly-butadiene (iii), be derived from polyether glycol (i), polyester polyol (ii) or hydroxyl terminated poly-butadiene at least a hydroxy-end capped or isocyanate-terminated polyurethane prepolymer is (iv) in (iii), be derived from end capped or isocyanate-terminated polyurethane-polyurea prepolymer of the amine of polyamine and/or polyureas prepolymer (v) and the olefinic unsaturated polyester (vi).
3. two component moisture-curable resin combinations of claim 2, wherein moisture-curable silylated resin (a) (1) is by polyether glycol (i), polyester polyol (ii), hydroxyl terminated poly-butadiene (iii), hydroxy-end capped polyurethane prepolymer (iv) or the end capped polyurethane-polyurea prepolymer of amine and/or the end capped polyureas prepolymer of amine (at least a and at least a isocyanato silane carries out silylanizing and obtains v), by isocyanate-terminated polyurethane prepolymer (iv) or isocyanate-terminated polyurethane-polyurea prepolymer and/or isocyanate-terminated polyureas prepolymer (v) with at least a selected from mercapto silane, primary amino silane, isocyanic ester-the reactive silane of secondary amino group silane and composition thereof carries out silylanizing and obtains, or (vi) carrying out hydrosilication with at least a silane containing hydrogen obtains by the olefinic unsaturated polyester.
4. two component moisture-curable resin combinations of claim 1, wherein moisture-curable silylated resin (a) (1) (iv) carries out the silylated polyurethane prepolymer that silylanizing obtains with vulcabond at least a by the hydroxy-end capped or isocyanate-terminated polyurethane prepolymer that is derived from polyether glycol (i).
5. two component moisture-curable resin combinations of claim 4, wherein use at least a isocyanato silane carry out hydroxy-end capped polyurethane prepolymer (iv) silylanizing and use the isocyanic ester-reactive silane of at least a selected from mercapto silane, primary amino silane, secondary amino group silane and composition thereof to carry out the silylanizing (iv) of isocyanate-terminated polyurethane prepolymer.
6. two component moisture-curable resin combinations of claim 1, wherein first component (a) contains one or more additional components (a) (2).
7. two component moisture-curable resin combinations of claim 1, wherein second component (b) contains softening agent (b) (2) and particulate matter (b) (2), and the amount that is present in the nonionogenic tenside (b) (3) in second component (b) is enough to provide the stable emulsion of softening agent (b) (2) and the steady suspension of particulate matter (b) (2).
8. two component moisture-curable resin combinations of claim 1, wherein nonionogenic tenside (b) (3) is selected from the multipolymer of Viscotrol C, oleic acid ethoxylate, alkylphenol ethoxylate, organosilicon and polyethers of multipolymer, the ethoxylation of polyoxyethylene glycol, polypropylene glycol, oxyethane and propylene oxide, and the mixture of aforementioned substances.
9. two component moisture-curable resin combinations of claim 2, wherein nonionogenic tenside (b) (3) is selected from the multipolymer of Viscotrol C, oleic acid ethoxylate, alkylphenol ethoxylate, organosilicon and polyethers of multipolymer, the ethoxylation of polyoxyethylene glycol, polypropylene glycol, oxyethane and propylene oxide, and the mixture of aforementioned substances.
10. two component moisture-curable resin combinations of claim 3, wherein nonionogenic tenside (b) (3) is selected from the multipolymer of Viscotrol C, oleic acid ethoxylate, alkylphenol ethoxylate, organosilicon and polyethers of multipolymer, the ethoxylation of polyoxyethylene glycol, polypropylene glycol, oxyethane and propylene oxide, and the mixture of aforementioned substances.
11. two component moisture-curable resin combinations of claim 4, wherein nonionogenic tenside (b) (3) is selected from the multipolymer of Viscotrol C, oleic acid ethoxylate, alkylphenol ethoxylate, organosilicon and polyethers of multipolymer, the ethoxylation of polyoxyethylene glycol, polypropylene glycol, oxyethane and propylene oxide, and the mixture of aforementioned substances.
12. two component moisture-curable resin combinations of claim 6, wherein nonionogenic tenside (b) (3) is selected from the multipolymer of Viscotrol C, oleic acid ethoxylate, alkylphenol ethoxylate, organosilicon and polyethers of multipolymer, the ethoxylation of polyoxyethylene glycol, polypropylene glycol, oxyethane and propylene oxide, and the mixture of aforementioned substances.
13. two component moisture-curable resin combinations of claim 7, wherein nonionogenic tenside (b) (3) is selected from the multipolymer of Viscotrol C, oleic acid ethoxylate, alkylphenol ethoxylate, organosilicon and polyethers of multipolymer, the ethoxylation of polyoxyethylene glycol, polypropylene glycol, oxyethane and propylene oxide, and the mixture of aforementioned substances.
14. two component moisture-curable resin combinations of claim 1 are mixed with tackiness agent, sealing agent or coating with described composition.
15. two component moisture-curable resin combinations of claim 2 are mixed with tackiness agent, sealing agent or coating with described composition.
16. two component moisture-curable resin combinations of claim 3 are mixed with tackiness agent, sealing agent or coating with described composition.
17. two component moisture-curable resin combinations of claim 4 are mixed with tackiness agent, sealing agent or coating with described composition.
18. two component moisture-curable resin combinations of claim 6 are mixed with tackiness agent, sealing agent or coating with described composition.
19. two component moisture-curable resin combinations of claim 7 are mixed with tackiness agent, sealing agent or coating with described composition.
20. two component moisture-curable resin combinations of claim 8 are mixed with tackiness agent, sealing agent or coating with described composition.
21. two component moisture-curable resin combinations of claim 9 are mixed with tackiness agent, sealing agent or coating with described composition.
22. two component moisture-curable resin combinations of claim 10 are mixed with tackiness agent, sealing agent or coating with described composition.
23. two component moisture-curable resin combinations of claim 11 are mixed with tackiness agent, sealing agent or coating with described composition.
24. two component moisture-curable resin combinations of claim 12 are mixed with tackiness agent, sealing agent or coating with described composition.
25. two component moisture-curable resin combinations of claim 13 are mixed with tackiness agent, sealing agent or coating with described composition.
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